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United States Patent |
5,064,922
|
Wamprecht
,   et al.
|
November 12, 1991
|
Copolymers containing amino groups and a process for their production
Abstract
The present invention relates to copolymers having a weight average
molecular weight (M.sub.w) of 1500 to 75,000, prepared from olefinically
unsaturated compounds and containing 0.1 to 4.5% by weight of primary
amino groups in the form of structural units corresponding to formula I
##STR1##
wherein Q is a saturated aliphatic-cycloaliphatic hydrocarbon radical of
the type obtained by removing the amino groups from an
aliphatic-cycloaliphatic diprimary diamine containing an amino group
attached to a primary carbon atom and an amino group attached to a
secondary or tertiary carbon atom.
The present invention also relates to a process for the production of these
copolymers.
Inventors:
|
Wamprecht; Christian (Krefeld, DE);
Pedain; Josef (Cologne, DE);
Blum; Harald (Krefeld, DE)
|
Assignee:
|
Bayer Aktiengesellschaft (Leverkusen, DE)
|
Appl. No.:
|
573611 |
Filed:
|
August 27, 1990 |
Foreign Application Priority Data
Current U.S. Class: |
526/262; 525/327.6 |
Intern'l Class: |
C08F 222/40; C08F 222/06 |
Field of Search: |
526/262
525/327.6
|
References Cited
U.S. Patent Documents
4426491 | Jan., 1984 | Gardner | 524/878.
|
4464522 | Aug., 1984 | Plum | 526/301.
|
4525521 | Jun., 1985 | DenHartog et al. | 524/517.
|
4659770 | Apr., 1987 | Vasta | 524/553.
|
4699936 | Oct., 1987 | Vasta | 523/400.
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Cheng; Wu C.
Attorney, Agent or Firm: Gil; Joseph C., Roy; Thomas W.
Claims
What is claimed is:
1. A copolymer which is readily soluble in organic solvents, has a weight
average molecular weight (M.sub.w) of 1500 to 75,000, is prepared from
olefinically unsaturated compounds and contains 0.1 to 4.5% by weight of
primary amino groups in the form of structural units corresponding to
formula I
##STR6##
wherein Q is a saturated aliphatic-cycloaliphatic hydrocarbon radical
obtained by removing the amino groups from an aliphatic-cycloaliphatic
diprimary diamine containing an amino group attached to a primary carbon
atom and an amino group attached to a secondary or tertiary carbon atom.
2. The copolymer of claim 1 which contains 0.3 to 3.0% by weight of primary
amino groups in the form of structural units corresponding to formula V
##STR7##
wherein R.sub.1 is hydrogen or a C.sub.1-4 alkyl radical,
R.sub.2 and R.sub.3 may be the same or different and represent a
difunctional, saturated, aliphatic hydrocarbon radical containing 1 to 6
carbon atoms, the sum of the number of carbon atoms in R.sub.2 and R.sub.3
being from 3 to 8,
R.sub.4 is hydrogen or a C.sub.1-4 alkyl radical,
R.sub.5 is a difunctional, saturated, aliphatic hydrocarbon radical
containing 1 to 4 carbon atoms and
n is 0 to 1.
3. The copolymer of claim 2 wherein
R.sub.1 is hydrogen or a methyl radical,
R.sub.2 and R.sub.3 may be the same or different and represent a
difunctional, saturated, aliphatic hydrocarbon radical containing 1 to 5
carbon atoms, the sum of the number of carbon atoms in R.sub.2 and R.sub.3
being from 4 to 6,
R.sub.4 is hydrogen or a methyl radical,
R.sub.5 is a difunctional, saturated, aliphatic hydrocarbon radical
containing 1 to 3 carbon atoms and
n is 0 or 1.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to new copolymers of olefinically unsaturated
monomers containing primary amino groups and to a process for the
production of these copolymers.
2. Description of the Prior Art
Copolymers of olefinically unsaturated monomers containing primary amino
groups are known. EP-A-0 101 962 for example describes polymers containing
primary amino groups, a process for their production and their use. These
aminofunctional polymers are produced by reacting a hydroxyl
group-containing ester of an .alpha.,.beta.-olefinically unsaturated mono-
or dicarboxylic acid and an dihydric alcohol (such as hydroxyethyl
acrylate) with a diisocyanate at an equivalent ratio of NCO to OH groups
of greater than 1:1 in a first step. This produces an
.alpha.,.beta.-olefinically unsaturated mono- or diisocyanate which, in a
second step, is subjected to radical polymerization with other monomers to
form an isocyanate-functional copolymer. In a third step, the isocyanate
groups of the copolymer are converted into ammonium salts by reaction with
excess mineral acid (concentrated HCl) and water with elimination of
CO.sub.2 and, in a fourth step, the ammonium salts are neutralized by the
addition of a base (methanolic KOH). Copolymers containing free amino
groups are obtained.
The disadvantage of this process is that the isocyanate-functional monomers
obtained in the first step are not completely uniform 1:1-adducts, which
can result in crosslinked products in the second step (the polymerization
step) unless an elaborate purification process has been carried out
beforehand. Another disadvantage lies in the very involved production of
the amino-functional polymers in a total of four reaction steps. Another
disadvantage of this known process is that because of the severe
hydrolysis and neutralization conditions (concentrated HCl, KOH), not only
are the isocyanate groups susceptible to hydrolysis, the (meth)acrylate
units are also susceptible to undergoing partial hydrolysis, resulting in
degradation of the polymer.
EP-A-0 179 954 describes two-component coating systems based on
amino-functional and epoxy-functional polyacrylate systems. In this case,
the amino-functional polymer is produced by preparing a
carboxyl-functional copolymer in a first step using (meth)acrylic acid as
the functional monomer together with other monomers. To introduce the
amino groups, this copolymer is reacted with propylene imine in a
ring-opening reaction accompanied by the formation of primary amino
groups. A serious disadvantage of this process is that propylene imine,
like ethylene imine, is an extremely dangerous substance which has been
proven to be carcinogenic in animal tests.
U.S. Pat. Nos. 4,659,770 and 4,699,936 describe amino-functional copolymers
which are used as binder components in two-component paints. They are
produced by initially synthesizing aminofunctional (meth)acrylate monomers
by the reaction of alkane diol di(meth)acrylates (such as hexane diol
diacrylate) with diamines in quantitative ratios which form 1:1 adducts
containing both free amino groups and also unsaturated (meth)acrylate
groups. These amino-functional monomers are then copolymerized with other
unsaturated monomers to obtain the amino-functional copolymers. The
disadvantage of this process is that difficulties are involved in the
production and processing of the amino-functional monomers. Thus,
relatively high molecular weight oligomers may also be formed in addition
to the desired 1:1 adducts. These oligomers promote gelation by acting as
unsaturated crosslinking agents in the subsequent copolymerization
process. Another disadvantage is that monomers containing both an
unsaturated, activated (meth)acrylate double bond and a free, primary
amino group are not stable in storage because both groups enter into an
addition reaction with one another, even at room temperature. This
addition reaction takes place considerably more quickly at elevated
temperatures, for example, at the stated reaction temperatures of
90.degree. to 100.degree. C., so that unwanted secondary reactions
resulting in gelled products can take place. Another particular
disadvantage of this process is that dark-colored products are always
formed when radical copolymerization processes initiated by organic
peroxides are conducted in the presence of amino groups. Because of their
color, these products are totally unsuitable, for example, for use as
binders in high-quality paints.
An object of the present invention is to provide new copolymers containing
primary amino groups which do not suffer from the above-mentioned
disadvantages of the prior art. It is a further object of the present
invention to provide copolymers containing amino groups which may be
readily obtained without complications from safe, inexpensive and
generally available raw materials and which are readily soluble in common
organic solvents to form colorless or only faintly colored polymer
solutions.
These objects may be achieved in accordance with the copolymers of the
present invention as described in detail hereinafter.
SUMMARY OF THE INVENTION
The present invention relates to copolymers having a weight average
molecular weight (M.sub.w) of 1500 to 75,000, prepared from olefinically
unsaturated compounds and containing 0.1 to 4.5% by weight of primary
amino groups in the form of structural units corresponding to formula I
##STR2##
wherein Q is a saturated aliphatic-cycloaliphatic hydrocarbon radical of
the type obtained by removing the amino groups from an
aliphatic-cycloaliphatic diprimary diamine containing an amino group
attached to a primary carbon atom and an amino group attached to a
secondary or tertiary carbon atom.
The present invention also relates to a process for the production of these
copolymers by reacting in a first reaction step,
a) 1 to 40 parts by weight copolymerizable anhydridefunctional monomers and
b) 60 to 99 parts by weight other copolymerizable monomers corresponding to
formulas (II), (III) and (IV)
##STR3##
wherein R.sub.6 is a linear or branched, aliphatic C.sub.1-18 hydrocarbon
radical or a C.sub.2-4 hydroxyalkyl radical,
R.sub.7 is hydrogen or a methyl, ethyl, chlorine or fluorine substituent,
R.sub.8 is an aromatic C.sub.6-12 hydrocarbon radical, a C.sub.2-7 alkoxy
group or an aminocarbonyl group which may contain a C.sub.1-6 alkyl
substituent which may further contain ether bridges at the nitrogen and
R.sub.9 corresponds to the definition given for R.sub.6, but need not be
identical with R.sub.6,
by radical-initiated copolymerization to form an anhydride-functional or
anhydride- and hydroxy-functional copolymer and, in a second reaction
step, reacting this copolymer with diamines corresponding to the formula
H.sub.2 N--Q--NH.sub.2
wherein Q is as defined above,
to form structural units corresponding to formula (I), wherein the quantity
of diamine is sufficient to provide an equivalent ratio of amino groups
attached to primary carbon atoms to acid anhydride groups of the copolymer
of at least 1:1 and wherein the components and the quantitative ratios in
which they are reacted are selected to provide copolymers having 0.1 to
4.5% by weight of primary amino groups.
DETAILED DESCRIPTION OF THE INVENTION
The copolymers according to the invention contain 0.1 to 4.5% by weight,
preferably 0.3 to 3.0% by weight of primary amino groups and have a weight
average molecular weight (M.sub.w, as determined by gel permeation
chromatography using polystyrene as the standard) of 1500 to 75,000,
preferably 2000 to 50,000 and more preferably 2500 to 30,000. The primary
amino groups are present in the copolymers in the form of structural units
corresponding to formula (I) above, preferably in the form of structural
units corresponding to formula (V)
##STR4##
wherein R.sub.1 is hydrogen or a C.sub.1-4 alkyl radical, preferably a
methyl radical,
R.sub.2 and R.sub.3 may be the same or different and represent a
difunctional, saturated, aliphatic hydrocarbon radical containing 1 to 6,
preferably 1 to 5 carbon atoms, the sum of the number of carbon atoms in
R.sub.2 and R.sub.3 being from 3 to 8, preferably 4 to 6,
R.sub.4 is hydrogen or a C.sub.1-4 alkyl radical, preferably hydrogen or a
methyl radical,
R.sub.5 is a difunctional, saturated, aliphatic hydrocarbon radical
containing 1 to 4, preferably 1 to 3 carbon atoms and
n is 0 or 1.
The copolymers according to the invention may be produced by the process
according to the invention. In this process, an intramolecular copolymer
A' containing carboxylic anhydride groups is prepared in a first reaction
step and is then converted into the amino-functional copolymer A)
according to the invention in a second step by reaction with suitable
diamines.
The intramolecular copolymer A' is prepared from a monomer mixture
containing
a) 1 to 40, preferably 2 to 30 parts by weight of copolymerizable monomers
containing anhydride groups and
b) 60 to 99, preferably 70 to 98 parts by weight of other copolymerizable
monomers corresponding to formulae (II), (III) and (IV).
Typical examples of monomers a) include itaconic anhydride and maleic
anhydride; maleic anhydride is preferred.
Particularly preferred monomers b) are those corresponding to the formulas
(II), (III) and (IV) wherein
R.sub.6 is a linear or branched, aliphatic C.sub.1-8 hydrocarbon radical or
a C.sub.2-4 hydroxyalkyl radical,
R.sub.7 is hydrogen or a methyl group,
R.sub.8 is an aromatic C.sub.6-12 hydrocarbon radical which may contain
aliphatic substituents, a C.sub.2-7 alkoxy group or an aminocarbonyl group
which may contain a C.sub.1-6 alkyl substituent which may further contain
ether bridges at the nitrogen and
R.sub.9 corresponds to R.sub.6.
Typical examples of suitable and preferred substituents R.sub.6 and R.sub.9
include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl,
n-hexyl, 2-ethylhexyl, n-octyl, n-decyl or n-dodecyl, 2-hydroxyethyl,
3-hydroxypropyl, 2-hydroxypropyl and 4-hydroxybutyl.
Typical examples of suitable and preferred substituents R.sub.7 include
hydrogen and methyl, ethyl, chlorine of fluorine substituents.
Typical examples of suitable and preferred substituents R.sub.8 include
those aliphatic radicals set forth for R.sub.6, except for methyl and
hydroxyalkyl radicals, and also phenyl, cyclohexyl, 2-, 3- and
4-methyl-phenyl, propoxy, n-butoxy or aminocarbonyl radicals.
Any mixtures of monomers a) and b) may be used for the production of the
copolymers A', although preferred copolymers A' are those produced from a
monomer mixture in which 5 to 50% by weight of component b) is based on
monomers free from ester groups corresponding to the above formula and
preferably 50 to 100% by weight of the monomers free from ester groups are
styrene.
The copolymers A' may be produced by copolymerization of the monomers by
known radical polymerization processes such as bulk or solution
polymerization. The monomers are copolymerized at temperatures of
60.degree. to 200.degree. C., preferably 80.degree. to 160.degree. C.
(when monomers containing hydroxyl groups are present, preferably at
80.degree. to 140.degree. C.) in the presence of radical formers and
optionally molecular weight regulators.
The copolymerization is preferably carried out in inert solvents at a
solids content of 30 to 95% by weight. Suitable solvents include esters
such as propyl acetate, butyl acetate, isobutyl acetate, sec.-butyl
acetate, amyl acetate, hexyl acetate, benzyl acetate, ethyl propionate,
butyl propionate, isobutyl isobutyrate, ethoxypropyl acetate, propylene
glycol methyl ether acetate, oxohexyl acetate (Exxate 600, available from
Exxon) and oxoheptyl acetate (Exxate 700, available from Exxon); ethers
such as diisopropyl ether, dibutyl ether, dioxane and dimethyl diglycol;
hydrocarbons such as gasoline, turpentine oil, solvent naphtha, turpenes,
hexane, heptane, octane, cyclohexane, toluene, xylene and ethyl benzene;
ketones such as methylethyl ketone, methylisobutyl ketone, methyl-n-amyl
ketone, methylisoamyl ketone, diethyl ketone, ethylbutyl ketone,
diisopropyl ketone, cyclohexanone, methyl cyclohexanone and isophorone;
and mixtures of these solvents.
Preferred solvents are those which boil at temperatures .gtoreq.110.degree.
C. under normal conditions and those which form an azeotrope with water
such as xylene, butyl acetate, solvent naphtha and oxohexyl acetate.
The copolymerization may be carried out continuously or discontinuously.
Typically, the monomer mixture and the initiator are uniformly and
continuously introduced into a polymerization reactor and, at the same
time, the corresponding quantity of polymer is continuously removed.
Copolymers which are substantially chemically uniform may advantageously
be produced. Copolymers which are substantially chemically uniform may
also be produced by introducing the reaction mixture at a constant rate
into a stirred tank without removing the polymer.
It is also possible initially to introduce part of the monomers, for
example in solvents of the type mentioned, and subsequently to add the
remaining monomers and auxiliaries either separately or together at the
reaction temperature.
In general, the polymerization is carried out under an excess pressure of 0
to 20 bar. The initiators are used in quantities of 0.05 to 15% by weight,
based on the total quantity of monomers. Suitable initiators are known and
include aliphatic azo compounds such as azodiisobutyronitrile,
azo-bis-2-methyl valeronitrile, 1,1'-azo-bis-1-cyclohexane nitrile and
2,2'-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides
such as acetyl, propionyl or butyryl peroxide, bromine-, nitro-, methyl-
or methoxy-substituted benzoyl peroxides and lauryl peroxides; symmetrical
peroxydicarbonates such as diethyl, diisopropyl, dicyclohexyl and
dibenzoyl peroxydicarbonate; tert.-butyl peroxy-2-ethyl hexanoate;
tert.-butyl perbenzoate; tert.-butyl phenyl peracetate; peroxycarbonates
such as tert.-butyl-N-(phenylperoxy)-carbonate and tert.-butyl-N-(2-, 3-
or 4-chlorophenylperoxy)-carbonate; hydroperoxides such as tert.-butyl
hydroperoxide and cumene hydroperoxide; and dialkyl peroxides such as
dicumyl peroxide, tert.-butylcumyl peroxide and di-tert.-butyl peroxide.
To regulate the molecular weight of the copolymers, regulators may be used
during their production such as tert.-dodecyl mercaptan, n-dodecyl
mercaptan and diisopropyl xanthogene disulfide. The regulators may be
added in quantities of 0.1 to 10% by weight, based on the total quantity
of monomers.
The solutions of the copolymers A' which accumulate during the
copolymerization reaction may be subjected to the modification reaction of
the second stage of the process without further working up. However, it is
also possible to free the copolymers from any residues of unreacted
monomers still present and solvent, if any, by distillation prior to s
conducting the second stage of the process.
To produce the amino functional copolymers A, the copolymers A' containing
carboxylic anhydride groups are modified with suitable diamines
corresponding to formula (VI)
H.sub.2 N--Q--NH.sub.2 (VI),
preferably formula VII
##STR5##
wherein Q, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and n have the
meanings and preferred meanings defined above.
Preferred diamines include 1-amino-1-methyl-4(3)-aminomethyl cyclohexane,
which is generally present in the form of a mixture of the 4- and
3-aminomethyl isomers, 1-amino-1-methyl-4-(4-aminobut-2-yl)-cyclohexane,
1-amino-1,2,2-trimethyl-3-(2-aminoethyl)-cyclopentane and
1-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane (IPDA).
However, other diamines may be used and include
1-amino-1-n-butyl-3-(4-aminobut-1-yl)-cyclopentane,
1-amino-1-ethyl-4-n-butyl-4-(4-aminobut-1-yl)-cyclohexane and
1-amino-1,2-dimethyl-3-ethyl-3-aminomethyl cyclopentane.
The production of diamines containing an amino group attached to a primary
carbon atom and an amino group attached to a tertiary carbon atom is
described, for example, in EP-A-0 153 561 (U.S. Pat. No. 4,613,685).
To carry out the modification process according to the invention, the
anhydride-functional copolymers A' and the diamines are used in quantities
corresponding to an equivalent ratio of amino groups attached to a primary
carbon atom to acid anhydride groups of at least 1:1, preferably 1:1 to
2:1, more preferably 1:1 to 1.5:1 and most preferably 1:1 to 1.2:1.
In the modification reaction of the second stage of the process the
anhydride ring is initially opened by the amino group attached to the
primary carbon atom with formation of a semiamide structure and
subsequently the ring is closed with elimination of water and formation of
an imide group. The second stage may be conducted in the presence of a
solvent. Suitable solvents are the solvents preferably used for the
production of the anhydride-functional copolymers A'.
In the process according to the invention, the diamine, which may be a
mixture of several diamines, is initially introduced (optionally together
with a solvent) and heated to temperatures of .gtoreq.80.degree. C. The
dissolved anhydride-functional copolymer is subsequently added at
temperatures of 80.degree. to 200.degree. C., preferably 100.degree. to
150.degree. C. The reaction may be conducted such that as the polymer is
added, the water of reaction is azeotropically distilled off on a water
separator. In one variant of the process, the total quantity of
anhydridefunctional copolymers may initially be added and the water of
reaction subsequently eliminated and distilled off, preferably
azeotropically.
Elimination of the water of reaction is continued at 110.degree. to
200.degree. C., preferably at 120.degree. to 150.degree. C., until either
the theoretical quantity of water has been eliminated or no more water is
eliminated. The elimination of water may be accelerated, for example, by
an inert gas stream which may be passed either through or over the
reaction mixture.
After the modification reaction, it is possible, if necessary, to remove
excess diamine from the end product, by brief distillation, preferably
azeotropic distillation with a suitable solvent such as xylene, butyl
acetate, solvent naphtha and oxohexyl acetate.
The molecular weights (M.sub.w) of the amino-functional copolymers A
substantially correspond to the molecular weights of the
anhydride-functional copolymers A', plus the calculated molecular weight
of the diamines used, minus the quantity of water eliminated.
The amino-functional copolymers A according to the invention are readily
soluble in organic solvents. They may be used, for example, as a binder or
binder component in solvent-containing paints, coating compositions,
sealing compositions, adhesives or printing inks.
In the following examples, all quantities in "parts" and "percent" are by
weight, unless otherwise indicated.
EXAMPLES
EXAMPLE 1
General procedure for the production of anhydride-functional copolymers
A'.sub.1 to A'.sub.10
Part I was introduced into a 4-liter reaction vessel equipped with a
stirrer, cooling and heating system and heated to the reaction
temperature. Part II and part III were then added at the same time; part
II was added over a total period of 2 hours and part III was added over a
total period of 2.5 hours. The reaction mixture was then stirred for 2
hours at the reaction temperature.
The reaction temperatures and the composition of parts I to III are set
forth in Table I together with the characteristic data of the copolymers
A' obtained.
TABLE I
__________________________________________________________________________
(Quantities in g)
Copolymers A'.sub.1
A'.sub.2
A'.sub.3
A'.sub.4
A'.sub.5
A'.sub.6
A'.sub.7
A'.sub.8
A'.sub.9
A'.sub.10
__________________________________________________________________________
Part I
Xylene 1,200
1,200
1,200
1,200
1,200
1,200
1,200
1,200
1,200
1,200
Part II
Ethyl acrylate
279
-- -- -- -- -- 312
-- -- --
Butyl acrylate
-- -- -- 657
-- -- -- -- -- 470
2-ethylhexyl-
328
-- -- -- -- -- -- 837
-- --
acrylate
Methyl methacrylate
493
411
-- 263
-- -- -- -- -- 34
Butyl methacrylate
-- -- 903
-- -- 903
575
-- 862
--
2-ethylhexyl-
-- 591
-- -- 903
-- -- -- -- --
methacrylate
Styrene 493
575
657
624
624
616
624
657
616
718
Maleic anhydride
49 66 82 99 115
123
131
148
164
34
Hydroxypropyl meth-
-- -- -- -- -- -- -- -- -- 386
acrylate
Part II
Tert. butylperoxy-2-ethyl
98 98 98 98 98 98 98 98 98 98
hexanoate (70%)
Xylene 60 59 60 59 60 60 60 60 60 60
Polymerization
125
125
125
125
125
125
125
125
125
125
temperature (.degree.C.)
Solids content (%)
55.6
55.9
55.4
55.2
55.5
55.3
54.7
54.6
55.7
55.5
Viscosity (23.degree. C.,
274
512
590
324
280
787
371
198
1193
1049
mPa .multidot. s)
__________________________________________________________________________
EXAMPLE 2
General procedure for the reaction of the anhydride-functional copolymers
A'.sub.1 to A'.sub.10 with diamines to form the amino-functional
copolymers A.sub.1 to A.sub.10
Part I was introduced into a 1 liter reaction vessel equipped with a
stirrer, cooling and heating system and heated to the reaction
temperature. Part II was then added with stirring over a period of 1.5
hours. After the addition of part II, the reaction mixture was heated to
the reflux temperature and heated on a water separator until the
theoretical quantity of water had been eliminated or until no more water
was eliminated. The amino-functional copolymer formed was then be adjusted
to the particular solids content required by distilling off solvent, if
necessary.
The compositions of parts I and II and also the reaction temperatures are
set forth in Table II which also sets forth the characteristic data of the
amino-functional copolymers obtained.
TABLE II
__________________________________________________________________________
(Quantities in g)
Copolymers A'.sub.1
A'.sub.2
A'.sub.3
A'.sub.4
A'.sub.5
A'.sub.6
A'.sub.7
A'.sub.8
A'.sub.9
A'.sub.10
__________________________________________________________________________
Part I
Xylene 200
200 200
200 200 200 200 200 200
200
1-amino-1-methyl-
-- -- 24 29 33 36 38 43 48 10
4(3)-aminomethyl
cyclohexane
1-amino-3-aminomethyl-
17 22 -- -- -- -- -- -- -- --
3,5,5-trimethyl
cyclohexane
Part II
Copolymer 500
500 500
500 500 500 500 500 500
500
A'.sub.1
A'.sub.2
A'.sub.3
A'.sub.4
A'.sub.5
A'.sub.6
A'.sub.7
A'.sub.8
A'.sub.9
A'.sub.10
Reaction temp. (.degree.C.)
100
120 100
100 100 100 100 100 100
100
Quantity of water
1.4
1.9 2.2
3.0 3.3 3.4 3.8 4.5 4.8
1.0
eliminated
Quantity of xylene
225
185 225
215 115 110 110 230 205
235
distilled off
Solids content (%)
59.7
54.8
60.1
59.6
50.6
50.2
50.1
61.3
60.0
60.1
Visc. (23.degree. C.,
7674
33790
4200
12100
29100
23800
13500
54200
5750
62870
mPa .multidot. s)
Contents of NH2
0.44
0.56
0.76
0.91
1.04
1.11
1.18
1.32
1.42
0.33
groups, based on
solid resin (%)
__________________________________________________________________________
Although the invention has been described in detail in the foregoing for
the purpose of illustration, it is to be understood that such detail is
solely for that purpose and that variations can be made therein by those
skilled in the art without departing from the spirit and scope of the
invention except as it may be limited by the claims.
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